Crucible for reacting materials to form molten liquids of different densities and provided with means for decanting such liquids separately



United States Patent Ofifice Cla'ence F. Hiskey and Jean A. Lamourenx, New York, N.Y., assigors to Transitio Metals & Chemicals, Inc., .Wallkill, N.Y., a corporation of Delawa'e Original application Apr. 30, 1956, SenNo. '581,343,

now Patent 'No. 2,889,218, dated June 2, 1959. Di-

`vided and this 'application June 4, 1958, Ser. No.

11 Claims. (Cl. 266-39) The principal object of the present invention is to provide a new, improved crucible for a continuous process for metallothermic reactions. This application is a division of our application Ser. No. 581343, filed April 30, 195 6, now Patent No. 2,889,218, granted June 2, 1959. For this purpose a special crucible is described which permits the continuous introduction of the metallothermic mixture and the continuous removal of slag and metal. Provision can be made in this crucible for the preheating of the reaction mixture prior to its being brought into the reaction zone and in addition provision can bemade for nduction heating of the crucible contents in the reaction and segregation zones. The specific details of this apparatus and process will be given after a description of the metallothermic reaction.

Metallothermic reactions are chemical reactions, exothermic in character, in which a more active metal displaces a less active one from one of its Chemical compounds. The classic example of such a reaction is the displacement of iron from its magnetic oxide by aluminum, according to the following equation:

In this reaction aluminum is the more active metal which displaces the iron from its oxide. This mixture of materials, after careful blending, may be gnited by means of an ignition charge'of ,appropriate composition. When ignited the reaction rapidly progresses through the body of the reaction mixture so that within'a matter of 20-60 seconds tonnage quantities of 'such a mixture may be caused to react. Now, when the metal and the particular oxide are appropriately chosen, the heat which is evolved is suificient to raise the temperature of the whole reaction mass to more than 2500' C. Thisis above the melting point of both the iron and the alumina so that theremixture which has been placed on top of the Essentially then, this method 'of operation' producesfa single batch of metal at atime. I There are many faults associated with this method .of operation. In order to get a maximum yield of 'reduced metal, theoretical considerations indicate that boththe oxide to be reduced'and the active metal be as finely divided as possible. This however, has a great disadvantage because there are likely to be variable amounts of gas-forming 'materials present in the reaction mixture, When the reaction commences these gaseous substances arequickly raised to very high temperatures andare ejected explosively along with molten slag and metal. As a consequence, there'is great danger in operating with` finely comminuted material. 'Even more than this is the fact that as the reactants ,are morefinely subdivided, it isfound that the rate of reaction of the mass increases, With finely atomized reducing metal and metallic oxides the reaction takes on an almost explosive character. In practice, therefore, it is customery to keep the reaction rate manageable. In our invention, fineness of particle size of the reactants, far from being a handicap, is one of the most desirable prerequisites.

A second fault of the batch process is the great thermal shock to which the crucible is subjected. In ordinary operation the crucible is at room temperature immediately prior to ignition of the reaction mass; within a half a minute after the reaction has been initiated the contents of the crucible have been raised to white heat; a minute or two later the contents of the crucible are emptied and the crucible is allowed to chill down. This rapid heating and cooling cycle produces checks and cracks in the cruciblelining materialand after a number of reaction processes this liner must be removed and replaced by a new one. Thus, the problem of maintenance of the crucible is an expensive and tirne-consuming operation.

A third fault of the batch process is the heat loss from the reaction mass occasioned by the use of a cold crucible. This chilling eifect leads to freezing of ,some of the slag at the crucible wall and at the air interface and also causes a higher Viscosity throughout the body of the I slag. In the more viscous slags, the unreacted materials' are less likely to dilfuse and hence much of the reagents remains unreacted and therefore goes to waste. This is particularly true ,when reducing .oxideszof niobium, tan; talum, titanium, and zirconium. The large' amount of heat lost as radiation from the top of the open crucible usually results in the solidification of the top surfaceof. i

action mass' becomes liquid. Since the alumina is less dense than the iron, and since they are not mutually solu ble, segregation occurs with 'the alumina layer floating on top of the liquid iron. By means of this process pure iron may be formed.

In the history of this process many other metals have been substtuted for the aluminum, i.e., magnesium, cal cium, sodium, potassium, etc.-, hereafter called reducing metals. Sirnilarly, many substitutions have been made for the iron oxide i.e., manganese oxide, chromium oxide, molybdenum oxide, tungsten oxide, Vanadium' oxide, niobium oxide, tantalum oxide, titanium oxide, etc., hereafter called metallic oxides, and in addition other metallic salts and compounds and metallic minerals have been reduced to their metallic state by this general type of reaction. 'Even more llustrations might be given but those given should suce to demonstrate the great utlity of this class of reaction.

The present state of the alt consists in filling magnesia or'other refractory crucibles with the reaction mixture,

' In the accorrpanying drawing illustratingoie suitable r I form of crucible: i Fig. 1 shows in sectional side View, a crucible suitable for carrying out the process of the present inventor''; Fig. 2 shows a sectional top view of the same on the broken line 2-2 of Fig. l; and i Fig. 3 is a similar view on the broken line 3-3 of Fg. l. i i -'The crucible in the form shown comprses a bottom wa 1l 10, a rear wall 11, :a front wall 12, end walls 8 and 9, and a top wall 13 The crucible, furthermore, sf

formed with a bathe 17 parallel to the end walls s a'nd, i v i 9 and extending from the bottom wall wand rear wall 11 terminating short of the front wall, thereby forming a reaction zone or chamber *16 between said bafe and' end wall -8, and a passage 18 between the front edge of the baffie 17 and front wall 12. Extending from the r front wall 12 and bottom wall.10, toward the rear Wall 11 is a second baflie 19 parallel to the bafiie 17, but termi; nating short of the rear wall 11, thereby forming a pas-' sage 20 between the baffies 17 and -19 and a passage around the rear edge of battle 19.' Extending from e p g wall 9 is a ba fi- The mo wa saw??? Ptented Ma a se e 11 and 12. Its lower end is spaced above the bottom wall 10, thus forming between baflles 23 and 19 a passage 23a. Between the lower end of the baffie 23 and the bottom wall is formed a chamber or quiet zone 22. Extending upwardly from the chamber 22, and between the baflie 23 and the end wall 9 is a passage 26. Passage 26 extends part of the way up and terminates well below the upper end of the batfle 2 3.

Extending outwardly from the upper end of passage 26 is a horizontal duct 26a from which extends downwardly to the lower end of the crucible, a duct 28. The ducts 26a and 28 are formed in the end wall 9.

Extending forwardly from the passage 2311 into wall 12 is a horizontal duct 23b disposed at a higher level than the duct 26a. Wall 12 is formed with a duct 24 extending downwardly from duct 23b to the underside of the crucible.

The top wall 13 is formed with an inclined through passage 14 adapted to admit a projecting rod 15 of the feed material described elsewhere herein. The feed rod 15 is shown as being molded and extruded by a die 31 as it is fed into the crucible, and may be heated as shown diagrammatically by a preheater 32 of any suitable construction. The crucible may be heated by electric induction from coils 29 which may be embedded in the walls of the crucible, in openings 30.

The rod 15 reaches part way into the reaction zone 16, and comprises the reaction charge, that is, finely divided reducing metal, metallic oxide, fluxing agent, etc., preferably in stoichiometric proportion, compressed into various shapes, the preferred one being a rod of indefinite length which emanates from the extrusion die 31. This rod in turn is fed as fast as it is formed through the opening 14 in the top wall 13 of the crucible. In this crucible the metallothermic mixture reacts to produce molten metal and slag. The rod is fed in at a rate equal to or slightly in excess of the rate at which the rod would burn linearly in order to avoid burning backward. In the reaction chamber 16 where the rod is injected, a violent and turbulent reaction occurs. This reaction zone is shielded from the rest of the contents of the crucible by means of the several baffles 17 and 19 which are built as part of the walls of the crucible. After the molten material passes around the baffles through the passages 18, 20 and 21, it comes into a quiet zone 22 of the crucible where segregation of the two molten layers occurs. Two ports are provided in the wall for the continuous flow of these two layers out of the crucible. The upper port 23b, 24 is the one out of which the slag flows. By reason of the J-shaped flow passage 23, 22, 26 in the crucible, the separate phases flow to their designated outlet ports. The crucible may be made of magnesia. Molten metal which is heavier than the slag, pours from ports 26a, 28, and the slag which is lighter rises in passage 23a and pours out of ports 23b, 24. The weight of molten metal in passage 26 is equal to the combined weights of molten metal and slag in passage 23a.

Another fault has to do with the large size of the crucible required for tonnage production. Any crucible used in a batch reaction must be about three times larger than that required to hold the liquified material. This requirement is due to the very low bulk density of the unreacted material as contrasted with the higher density of the liquid material.

There are a great many other faults which might be adduced against batch operation, but the ones listed above are the more important to illustrate the need for a continuous process such as ours which will reduce cost and increase percentage yields of desired metals.

Our process has been achieved in the following manner: The reaction charge, i.e., finely divided reducing metal, metallic oxide, fluxing agent, etc., is compressed into various shapes, such as rays, sheets, pellets or powder, the preferred one being a rod of indefinite length which emanates from an extrusion die. This rod in turn is fed as fast as it is formed through a hole in the top of a specially constructed magnesia crucible. In this crucible, the metallothermic mixture reacts to produce molten metal or alloy or slag. The rod is fed in at a rate equal to or slightly in excess of the rate at which the rod would burn linearly in order to avoid burning backward. In the region where thereaction rod is injected a violent and turbulent reaction occurs. That reaction zone isshielded from the rest of the contents of the crucible by means of several bafiies which are built as part of the walls of the crucible. After the molten material passes around the baffles, it comes into a quiet zone of the crucible where separation of the mixture into two molten layers occurs. Two ports are provided in the wall for the continuous flow of these two layers out of the crucible. The upper port is the one out of which the slag flows and the lower port is the one from which the metal phase flows. The separated phases flow through their designated ports as explained above. After flowing from the port, the metal may be cast into ingots or handled in any other desired way.

Having now described the general characteristics of our invention, it is pertinent to describe special and critical details.

In the first place, the linear rate of burning of the rods mentioned above is primarily a function of two variables and must be determined empirically for each specific charge. These variables are: (a) the composition of the mixture and (b) the particle size of the Components of that mixture. In other words, our experience indicates that for a given particle size the rate of burning varies with the metallic oxide to be reduced and with the reducing metal. On the other hand, for a particular composition, the rate of burning increases as the particle size decreases. For example, in one alumnum and iron oxide mixture studied, we found that by merely varying the particle size from 20 mesh to 325 mesh it was possible to increase the burning rate from one cm./sec. with the coarsest material to as much as 8 cm./sec. with the finest. Consequently in each case before starting a production run it is imperative to measure the burning rate and adjust the extrusion or feed rate to at least 25 or percent faster.

The second critical item involves the start-up operation. We have found it impossible to begin metal production by using a cold crucible and igniting the rod within it. The crucibles invariably plugged because the ports became clogged with solidified slag. On the other hand,

i we found that heating with a burner through one of the ports, first with air and oil and finally with an oxyacetylene torch until the inside of the crucible was brought to a temperature sufficient to keep the metal and slag in a l'quid state was the preferred method of starting opera tion. If at that temperature a rod of the metallothermic mixture is inserted into the `hot crucible it immediately begins to burn. This temperature will naturally vary with each charge composition.

As the crucible fills with the molten metal and slag the manometric leg is filled. When sufiicient metal has been formed so that the leg is sealed with molten metal then the slag is prevented from entering the metal leg. A small amount of slag is ejected through the metal port before any metal comes through, after which no more slag can get into that leg.

A third factor to be considered in any production is the hold-up time in the crucible. This time is determined by the crucible capacity and the feed rate. For the slower reductions this time should be made longer, with the slag kept in a very fluid condition. For the faster reductions hold-up times as short as three minutes were suitable for complete reaction. As an example, ordinary Thermit" mix was studied using a %-inch feed rod with a feed rate of four pounds per minute and with a hold-up time of only three minutes. In spite of this short time, it was'adequate to achieve essentially stoichometric yields.

Another experiment repeated under similar conditions using ferrous columbate (columbite ore) in place of the iron oxide gave a 50% yield. When the crucible was enlarged to provide a hold-up time of 5.3 minutes an 85% yield was achieved;

Finally, details of crucible preparation should be described. We have used magnesia almost exclusively to date. 'Since the crucibles have small Capacity, 'usually with'a liollow Volume between one and ten liters, their overall dimensions are relatively small. We have used walls six inches thick which were rammed into shells made of sheet iron. After the bottom part of the crucible was rammed in, inserts for the b'afiies and the manornetric leg were made before the sides were ramned in. The plate creating the manometrc leg was arbitrarily set at /2 inch above the crucible floor. We are not restricted to this dimensions, however. Next, a snug fittng magnesia cover was prepared. The port holes and the feed hole were made by inserting 'wooden plugs during the ramming' stages and'later withdrawn. The port hole for the slag is placed at least two nches below the cover while the metal port is even lower. i The spacing of these holes ma be made in strict accordance with the density considerations of the particular mixture being processed. This is most desirable'. However, some departure from these conditions may be made and yet have the system operable. After drying with slow heat and then with high heat, the crucibles are put into operation. V

Having thus summarized the details of operation we now intend to review the advantages which accrue from our process.

(a) The apparatus is very small and cheap relative to the quantities of metal made. For example, with a feed rate of 4 1b./min. one can process as much as three tons per 24 hour day in a crucible whose hold-up Volume is only 12 to 15 pounds. The operation can continue until the crucible finally fails, which will take weeks.

(b) The thermal Shock is avoided because the crucible 'can be slowlyheated and once brought to Operating temperature maintained there until shut down.

(c) There is no danger from explosion due to trapped gases, to products which evolve gas on thermal decom- Weclaim: v

g 1. A-cruciblecomprising a bottom wall, front and i rear walls extending upwardlyfrom the bottom wall, end

extending forwardly from the rear wall, and upwardly from the bottom wall, and spaced from one end wall forming therewith a reaction zone in the crucible and said first baflieterminating short of the front wall, thereby` t forming a first passage around the front edge of said first battle; a second bafiie extending upwardly from the bottom wall and rearwardly from the front wall and spaced' from the first baffle forming therewith a second passage communicating with the first passage, said second bafiie terminating short of the rear wallforming a third pasposition or because of the fineness of subdivision of the reagent material because the reacting materials are injected in comparatively small quantities and give rise to comparably smaller quantities of gases which pass freely through the ports.

(d) Temperatures very much in excess of those pro duced by the heat of the reaction are easily achieved by two methods which may be used in conjunction with each other or separately. For example, by preheating the rod to a temperature just under the melting point of the reducing metal, we have raised the resulting temperature in the liquid metal as much as 600 C. In another experi ment we embedded a water-cooled copper coil in the walls of the crucible, ramming the magnesia into a Transite shell. Then by induction heating we were able to add an additional 500 C. to the melt. Indeed, with the two additional sources of heat, the temperature limit attainable is restricted only by the melting point of the crucible liner. The amount of heat added by either or both of these methods will be determined by the temperature sought and the exothermic heat of reaction of the charge.

(e) The entire operation may be made completely automatic.

While we have herein described one form in which our invention may be embodied, it will be understood that the Construction thereof and the arrangements of the various parts, as well as the composition of the reaction mixture, may be altered without departing from the spirit and scope thereof. Furthermore, we do not wish it to be construed as limiting our invention to the specific embodiment described, excepting as it may be limited in the appended claims.

sage communicating with the second passage, a third bafiie interconnecting said front and rear walls, and spaced from the second bafiie and from said other end wall, thereby forming a fourth passage between the third baflie and the second bafile, and a fifth passage at the lower end of the third baflle, and a sixth passage between the third baifie and said other. end wall, said other end wall being formed with a first duct communicating with the sixth passage, and with a second duet extending downwardly from the first duct to the underside of the crucible, said front wall being forme d with a third duct extending from the fourth passage and disposed at a level higher than the level of the first duct, and said front wall being formed with a fourth duct extending downwardly from the third duct to the underside of said crucible.

2. A crucible comprsing a bottom wall, opposed walls extending upwardly from the bottom wall, and end walls extending upwardly from the bottom wall and interconnecting said opposed walls, a bafe extending from one opposed wall and from the bottom wall, and terminating short of the other opposed wall, forming a reaction zone between said baflie and said one end wall, and a first passage between said baffle and the other opposed wall, a second baflie extending upwardly from the bottom Wall and from said other opposed wall, and terminating short of the first opposed wall forming a second passage communicating with the first passage, and a third passage between the second bafiie and said first opposed wall communicating with the second passage, a third baffie interconnecting said opposed walls and terminating short of the bottom wall, forming a fourth passage between the second and third bafiies and communicating with the third passage, and a fifth passage beneath the third baflie, and a sixth passage between the third baflle and the other end wall, and ducts communicating with the fourth and sixth passages respectively to per-mit material to flow downwardly from said passages, the duet communicating with the fourth passage being at a higher levelthan the duct communicating with the sixth passage.

' 3. The combination of claim 2, said crucible being provided with a top wall and being formed with an inlet opening leading to the upper end of the reaction zone.

4. The combination of claim 3, in combination with means within the crucible walls for heating said crucible.

5. The combination of claim 4, in combination with means to continuously feed material through said opening.

6. The combination of claim 5, in combination with means to preheat said material as t is fed to said opening.

7. A crucible comprising a bottom wall, end' walls, front and rear walls and spaced staggered transverse bafes in the crucible extending up from the bottom, wall, each baie extending from a front or rear wall toward and terminating short of the opposite wall, and providing a reaction chamber at one end of the crucible and a tortuous passage between and around one or more of said baflies and communicating at one end with said reaction chamber, said crucible being formed with a flow passage comprising a first portion and a second portion connected at their lower ends, the first portion extending to a higher level than the second portion and communicating with the other end of said tortuous passage, a wall of said crucible being forned with an outlet communicating with said first portion at a level above the upper end of the second portion and a wall of said crucible being formed with a second outlet communicating with the second portion at a level below the first outlet, said tortuous passage communicatng with said chamber and with first portion, throughout its height.

8. A crucible comprising outer walls and provided with an opening adjacent one end to receive reaction mixture, said crucible being formed with a reaction chamber at said end communicating with said opening for receiving material fed through said opening, said crucible being provided with a first passage communicating at one end, throughout its height, with said chamber to receive liquid materials from said chamber, said crucible being formed with a flow passage having a first portion and a second portion connected at their lower ends, the first portion extending to a higher level than the second portion and communicating throughout its height with the other end of said first passage, and said crucible being forrncd with an outlet in the first portion at a level above the second por- References Cited in the file of this patent UNITED STATES PATENTS 2,572,489. Jordan Oct. 23, 1951 2,665,223 Clough et al Jan. 5, 1954 2,692,196 Hulrne Oct. 19, 1954 2,741,556 Schwartz Apr. 10, 1956 2,788,204 Kallng et al Apr. 9, 1957 OTHER REFERENCES Elements of Chemical Engineering, Badger and Mc- Cabe, pp. 20-23, 1936. 

